JP5277813B2 - Method for producing fluorinated propene - Google Patents

Method for producing fluorinated propene Download PDF

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JP5277813B2
JP5277813B2 JP2008233878A JP2008233878A JP5277813B2 JP 5277813 B2 JP5277813 B2 JP 5277813B2 JP 2008233878 A JP2008233878 A JP 2008233878A JP 2008233878 A JP2008233878 A JP 2008233878A JP 5277813 B2 JP5277813 B2 JP 5277813B2
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trifluoropropene
tetrafluoropropene
pentafluoropropane
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JP2010064990A (en
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秀男 浜崎
泰雄 日比野
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Central Glass Co Ltd
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Priority to MX2011002191A priority patent/MX2011002191A/en
Priority to PCT/JP2009/065477 priority patent/WO2010029893A1/en
Priority to EP09813039.6A priority patent/EP2327680B1/en
Priority to US13/062,560 priority patent/US8487144B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen

Abstract

There is provided according to the present invention a process for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene, including: reacting 1,1,1,3,3-pentafluoropropane with hydrogen chloride in a gas phase in the presence of a solid catalyst. By the use of a specific solid catalyst such as a catalyst in which chromium is supported on alumina or activated carbon or an alumina catalyst, the 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene can be obtained with high yield from the 1,1,1,3,3-pentafluoropropane, which can be commercially available or prepared on an industrial scale.

Description

本発明は、機能性材料、生理活性物質の中間原料、溶剤、洗浄剤、発泡剤、冷媒、エアゾール、プロペラント、エッチャー等として有用な１−クロロ−３，３，３−テトラフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法に関する。   The present invention provides 1-chloro-3,3,3-tetrafluoropropene or 1 useful as a functional material, an intermediate raw material of a physiologically active substance, a solvent, a cleaning agent, a foaming agent, a refrigerant, an aerosol, a propellant, an etcher, or the like. , 3,3,3-tetrafluoropropene.

１−クロロ−３，３，３−トリフルオロプロペンの製造方法は、１，１，１−トリフルオロプロパンを塩素化して得られた１，１，１−トリフルオロ−３，３−ジクロロプロパンをアルコール性アルカリで脱塩化水素する方法（非特許文献１）、３，３，３−トリフルオロプロピンに塩化水素を付加反応させる方法（非特許文献２）、３−クロロ−１，１，１−トリフルオロ−３−ヨードプロパンのエタノール性水酸化カリウム（ＫＯＨ）による脱ヨウ化水素反応方法（非特許文献３）、１，３，３，３−テトラクロロプロペンあるいは１，１，３，３−テトラクロロプロペンを液相加圧下無触媒でフッ素化する方法（特許文献１）、または液相にてフッ素化触媒不在／存在下、１，１，１，３，３−ペンタクロロプロパンをフッ化水素によりフッ素化する方法（特許文献２、３）等が報告されている。
Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，６４，１９４２，１１５８． Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５２，３４９０． Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５３，１１９９． 米国特許第５，６１６，８１９号明細書 特開平８−１０４６５５号公報 特開平８−２３９３３４号公報 The method for producing 1-chloro-3,3,3-trifluoropropene comprises 1,1,1-trifluoro-3,3-dichloropropane obtained by chlorinating 1,1,1-trifluoropropane. A method of dehydrochlorination with an alcoholic alkali (Non-patent document 1), a method of adding 3,3,3-trifluoropropyne to hydrogen chloride (Non-patent document 2), 3-chloro-1,1,1- Dehydroiodination reaction method of trifluoro-3-iodopropane with ethanolic potassium hydroxide (KOH) (Non-patent Document 3), 1,3,3,3-tetrachloropropene or 1,1,3,3- Method of fluorinating tetrachloropropene without catalyst under pressure in liquid phase (Patent Document 1), or 1,1,1,3,3-pentachloropropane in hydrogen fluoride in the absence / presence of fluorination catalyst in liquid phase By How to fluorination (Patent Documents 2 and 3) have been reported.
J. et al. Am. Chem. Soc. 64, 1942, 1158. J. et al. Chem. Soc. , 1952, 3490. J. et al. Chem. Soc. , 1953, 1199. US Pat. No. 5,616,819 JP-A-8-104655 JP-A-8-239334

非特許文献１または３で報告された方法は、アルカリ分解により脱ハロゲン化水素することから廃棄物となるアルカリ金属塩を等モル量発生させ、非特許文献２または３で報告されている方法では３，３，３−トリフルオロプロピンや３−クロロ−１，１，１−トリフルオロ−３−ヨードプロパンなどの原料を大量に入手することが困難であるという問題がある。また、特許文献１〜３に開示された方法は、原料は比較的容易に入手できるものの目的生成物の選択率を高くするのは困難で収率が低いという問題が窺える。そこで、本発明では、工業的規模で効率的に生産できる１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法を提供する。   In the method reported in Non-Patent Document 1 or 3, the method described in Non-Patent Document 2 or 3 generates an equimolar amount of an alkali metal salt that becomes waste because it is dehydrohalogenated by alkali decomposition. There is a problem that it is difficult to obtain a large amount of raw materials such as 3,3,3-trifluoropropyne and 3-chloro-1,1,1-trifluoro-3-iodopropane. Further, the methods disclosed in Patent Documents 1 to 3 have a problem that although the raw materials can be obtained relatively easily, it is difficult to increase the selectivity of the target product and the yield is low. Therefore, the present invention provides a method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene that can be efficiently produced on an industrial scale.

本発明者らは、工業的規模で入手できる物質を原料とする１−クロロ−３，３，３―テトラフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法について検討した。その結果、固体触媒の存在下で１，１，１，３，３−ペンタフルオロプロパンと塩化水素を混合して反応させることにより、１−クロロ−３，３，３−テトラフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンが得られること見いだし、本発明に到達した。   The present inventors examined a method for producing 1-chloro-3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene using a material available on an industrial scale as a raw material. As a result, 1,1,1,3,3-pentafluoropropane and hydrogen chloride were mixed and reacted in the presence of a solid catalyst, whereby 1-chloro-3,3,3-tetrafluoropropene or 1,1 It was found that 3,3,3-tetrafluoropropene was obtained, and the present invention was reached.

本発明は次の通りである。
［１］気相中において固体触媒存在下１，１，１，３，３−ペンタフルオロプロパンを塩化水素と反応させることからなる１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［２］固体触媒が、アルミニウム、クロム、ジルコニウム、チタンおよびマグネシウムからなる群より選ばれる少なくとも１種の金属の金属酸化物である［１］に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［３］固体触媒が、アルミニウム、クロム、チタン、マンガン、鉄、ニッケル、コバルト、マグネシウム、ジルコニウムおよびアンチモンからなる群より選ばれる少なくとも１種の金属の化合物またはその混合物を担体に担持した担持触媒である［１］に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［４］担体が、アルミニウム、クロム、ジルコニウム、チタンおよびマグネシウムからなる群より選ばれる少なくとも１種の金属の金属酸化物または活性炭である［３］に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［５］１，１，１，３，３−ペンタフルオロプロパンが、１，１，１，３，３−ペンタフルオロプロパンと１−クロロ−３，３，３−トリフルオロプロペンの混合物として反応領域に供給される［１］〜［４］のいずれかに記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［６］１，１，１，３，３−ペンタフルオロプロパンが、［１］に記載の製造方法による生成物から回収された１，１，１，３，３−ペンタフルオロプロパンまたは１−クロロ−３，３，３−トリフルオロプロペンを含む［１］〜［５］のいずれかに記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。
［７］少なくとも原料の一部が１，１，１，３，３−ペンタフルオロプロパンと１−クロロ−３，３，３−トリフルオロプロペンを含む共沸混合物である［１］〜［６］のいずれかに記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 The present invention is as follows.
[1] 1-chloro-3,3,3-trifluoropropene or 1,3 comprising reacting 1,1,1,3,3-pentafluoropropane with hydrogen chloride in the gas phase in the presence of a solid catalyst , 3,3-Tetrafluoropropene production method.
[2] The 1-chloro-3,3,3-tri described in [1], wherein the solid catalyst is a metal oxide of at least one metal selected from the group consisting of aluminum, chromium, zirconium, titanium, and magnesium. A method for producing fluoropropene or 1,3,3,3-tetrafluoropropene.
[3] A supported catalyst in which at least one compound of a metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, cobalt, magnesium, zirconium and antimony or a mixture thereof is supported on a support. A method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to [1].
[4] 1-Chloro-3,3,3- according to [3], wherein the carrier is a metal oxide or activated carbon of at least one metal selected from the group consisting of aluminum, chromium, zirconium, titanium and magnesium. A method for producing trifluoropropene or 1,3,3,3-tetrafluoropropene.
[5] 1,1,1,3,3-pentafluoropropane reacts as a mixture of 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene The method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to any one of [1] to [4].
[6] 1,1,1,3,3-pentafluoropropane or 1,1,1,3,3-pentafluoropropane or 1-chloro recovered from the product obtained by the production method according to [1] 1-Chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to any one of [1] to [5], including 3,3,3-trifluoropropene Manufacturing method.
[7] At least a part of the raw material is an azeotropic mixture containing 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene [1] to [6] A process for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to any one of the above.

本明細書では、異性体を有する化合物において、異性体の種類を明示しない場合はすべての異性体の名称またはそれらの異性体の混合物を意味するものとし、例えば、１−クロロ−３，３，３―テトラフルオロプロペンは、シス−１−クロロ−３，３，３―テトラフルオロプロペンもしくはトランス−１−クロロ−３，３，３―テトラフルオロプロペンまたはこれらの異性体の混合物を意味する。同様に、１，３，３，３−テトラフルオロプロペンは、シス−１，３，３，３−テトラフルオロプロペンもしくは１，３，３，３−テトラフルオロプロペンまたはこれらの異性体の混合物を意味する。   In the present specification, in the case of a compound having an isomer, when the type of isomer is not specified, it means the name of all isomers or a mixture of isomers, for example, 1-chloro-3,3, 3-Tetrafluoropropene means cis-1-chloro-3,3,3-tetrafluoropropene or trans-1-chloro-3,3,3-tetrafluoropropene or a mixture of these isomers. Similarly, 1,3,3,3-tetrafluoropropene means cis-1,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene or a mixture of these isomers To do.

本発明の方法は、特定の触媒を使用することで１−クロロ−３，３，３−トリフルオロプロペン及び１，３，３，３−テトラフルオロプロペンを収率よく製造できる上に、原料として工業的に生産されている１，１，１，３，３−ペンタフルオロプロパンを採用することからその入手に困難をきたすことは無く、工業的な製造方法として極めて有効な方法である。   The method of the present invention can produce 1-chloro-3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene in a high yield by using a specific catalyst, Since 1,1,1,3,3-pentafluoropropane produced industrially is employed, there is no difficulty in obtaining it, and this is an extremely effective method as an industrial production method.

本発明は、気相中において固体触媒存在下、１，１，１，３，３−ペンタフルオロプロパンを塩化水素と反応させることを特徴とする１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造法である。当然、１−クロロ−３，３，３−トリフルオロプロペンと１，３，３，３−テトラフルオロプロペンを併せて製造する方法でもある。   The present invention relates to 1-chloro-3,3,3-trifluoropropene characterized by reacting 1,1,1,3,3-pentafluoropropane with hydrogen chloride in the presence of a solid catalyst in a gas phase. Alternatively, it is a method for producing 1,3,3,3-tetrafluoropropene. Naturally, it is also a method for producing 1-chloro-3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene together.

本発明の原料となる１，１，１，３，３−ペンタフルオロプロパンは、どのような方法で製造されたものでもよい。公知の方法としては、１，１，１，３，３−ペンタクロロプロパンや１−クロロ−３，３，３−トリフルオロプロペンなどを触媒の存在下液相または気相においてフッ化水素と反応させる方法があり、このような方法で工業的規模で製造されており、購入して使用することもできる。   The 1,1,1,3,3-pentafluoropropane used as the raw material of the present invention may be produced by any method. As a known method, 1,1,1,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoropropene, or the like is reacted with hydrogen fluoride in the liquid phase or gas phase in the presence of a catalyst. There are methods, which are manufactured on an industrial scale by such methods and can be purchased and used.

本発明にかかる固体触媒は、金属酸化物、金属フッ素化酸化物または金属担持触媒である。
金属酸化物としては、アルミニウム、クロム、ジルコニウム、チタンまたはマグネシウムの金属酸化物が好ましい。また、これらからなる群より選ばれる少なくとも一種の金属を含む複合金属酸化物であってもよい。これらの酸化物は、その酸素原子の一部または全部をフッ化水素やフッ素含有有機化合物によりフッ素原子で置換したものであってもよく、フッ素原子で置換したものが好ましい。特に活性アルミナをフッ化水素、フッ素含有有機化合物等でフッ素化したフッ素化アルミナが好ましい。本明細書においては、この様に金属酸化物の酸素原子の一部または全部をフッ化水素やフッ素含有有機化合物によりフッ素原子で置換した金属フッ素化酸化物をも金属酸化物と称することがある。 The solid catalyst according to the present invention is a metal oxide, a metal fluorinated oxide or a metal-supported catalyst.
As the metal oxide, a metal oxide of aluminum, chromium, zirconium, titanium, or magnesium is preferable. Moreover, the composite metal oxide containing at least 1 type of metal chosen from the group which consists of these may be sufficient. These oxides may be those in which some or all of the oxygen atoms are substituted with fluorine atoms with hydrogen fluoride or a fluorine-containing organic compound, and those with fluorine atoms are preferred. Particularly preferred is fluorinated alumina obtained by fluorinating activated alumina with hydrogen fluoride, a fluorine-containing organic compound or the like. In the present specification, a metal fluorinated oxide in which part or all of the oxygen atoms of the metal oxide are substituted with fluorine atoms with hydrogen fluoride or a fluorine-containing organic compound is sometimes referred to as a metal oxide. .

金属酸化物は、市販品を使用することができる他、触媒調製法として公知の方法で調製できる。金属塩水溶液からアンモニアなどでｐＨを調整して水酸化物を沈殿させ、沈殿を乾燥または焼成して金属酸化物が調製される。得られた金属酸化物は粉砕または成形することもできる。例えば、アルミナは、通常、アルミニウム塩水溶液からアンモニアなどを用いて生じさせた沈殿を成型・脱水させて得られる。触媒担体用あるいは乾燥用として市販されているγ−アルミナを好ましく使用できる。チタニア、ジルコニアなども同様の方法で調製することができ、市販品を使用できる。また、これらの金属酸化物は共沈法などで調製した複合酸化物としても使用できる。担持される金属の種類、量および担持の方法などは触媒の技術分野における知識に基づいて行うことができる。また、後記する活性炭への担持についての説明に準じて行うことができる。     The metal oxide can be a commercially available product or can be prepared by a known method as a catalyst preparation method. The metal oxide is prepared by adjusting the pH of the metal salt aqueous solution with ammonia or the like to precipitate a hydroxide, and drying or baking the precipitate. The obtained metal oxide can be pulverized or molded. For example, alumina is usually obtained by molding and dehydrating a precipitate generated from an aluminum salt aqueous solution using ammonia or the like. Commercially available γ-alumina for catalyst support or drying can be preferably used. Titania, zirconia and the like can be prepared in the same manner, and commercially available products can be used. These metal oxides can also be used as composite oxides prepared by a coprecipitation method or the like. The kind and amount of the metal to be supported, the method of supporting, and the like can be performed based on knowledge in the technical field of catalysts. Moreover, it can carry out according to the description about the carrying | support to activated carbon mentioned later.

本発明の担体の態様としては、前記したアルミナ、クロミア、ジルコニア、チタニア、マグネシア等またはそれらの金属酸化物をフッ素化して酸素原子の一部または全部をフッ素原子で置換したフッ素化酸化物を選ぶことができる。これらのなかでアルミナ、特に活性アルミナをフッ素化して調製されるフッ素化アルミナが好ましい。   As the embodiment of the carrier of the present invention, the above-mentioned alumina, chromia, zirconia, titania, magnesia or the like or a fluorinated oxide in which a part or all of oxygen atoms are substituted with fluorine atoms by fluorinating those metal oxides is selected. be able to. Of these, fluorinated alumina prepared by fluorinating alumina, particularly activated alumina, is preferred.

本発明の担体のひとつの態様として活性炭を選ぶことができ、活性炭としては、木炭、椰子殻炭、パーム核炭、素灰等を原料とする植物系、泥炭、亜褐炭、褐炭、瀝青炭、無煙炭等を原料とする石炭系、石油残滓、オイルカーボン等を原料とする石油系、、またはポリ塩化ビニリデン等を原料とする合成樹脂系がある。これらの活性炭から選択し使用することができ、たとえば椰子殻炭（日本エンバイロケミカル製粒状白鷺GX、SX、CX、XRC、東洋カルゴン製ＰＣＢ等）が挙げられる。形状、大きさ等は反応器の大きさに適合すればよく、球状、円柱状、繊維状、粉体、ハニカム状の各種の形状から選択することができる。   Activated carbon can be selected as one embodiment of the carrier of the present invention, and as activated carbon, plant based on charcoal, coconut shell charcoal, palm kernel charcoal, raw ash, etc., peat, sublignite, lignite, bituminous coal, anthracite For example, there are coal-based using petroleum as a raw material, petroleum-based using petroleum residue, oil carbon and the like, or synthetic resin-based using polyvinylidene chloride as a raw material. These activated carbons can be selected and used, for example, coconut shell charcoal (Nippon Enviro Chemical's granular white straw GX, SX, CX, XRC, Toyo Calgon PCB, etc.). The shape, size, and the like may be adapted to the size of the reactor, and can be selected from various shapes such as a spherical shape, a cylindrical shape, a fibrous shape, a powder shape, and a honeycomb shape.

これらの担体に担持する金属としては、クロム、チタン、アルミニウム、マンガン、ニッケル、コバルト、チタン、鉄、銅、亜鉛、モリブデン、ジルコニウム、ニオブ、タンタル、イリジウム、錫、ハフニウム、バナジウム、マグネシウム、リチウム、ナトリウム、カリウム、カルシウム、アンチモンの中から選ばれる１種または２種以上の金属が挙げられる。これらのうち、アルミニウム、クロム、チタン、マンガン、鉄、ニッケル、コバルト、マグネシウム、ジルコニウムまたはアンチモンが好ましい。また、これらの金属のうちクロム単独またはクロムと含む複合系が好ましく、例えば、クロム／アルミニウム、クロム／チタン、クロム／鉄などが挙げられる。触媒の調製にあたっては、これらの金属の硝酸塩、酸化物、フッ化物、塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化物、オキシフッ化塩化物等を担持する。これらの金属の化合物は特に硝酸塩または塩化物として用いるのが好ましく、具体的には、硝酸クロム、塩化クロムなどが好適である。   The metals supported on these carriers include chromium, titanium, aluminum, manganese, nickel, cobalt, titanium, iron, copper, zinc, molybdenum, zirconium, niobium, tantalum, iridium, tin, hafnium, vanadium, magnesium, lithium, One or more metals selected from sodium, potassium, calcium, and antimony are listed. Of these, aluminum, chromium, titanium, manganese, iron, nickel, cobalt, magnesium, zirconium or antimony are preferred. Of these metals, chromium alone or a composite system containing chromium is preferable, and examples thereof include chromium / aluminum, chromium / titanium, and chromium / iron. In preparing the catalyst, nitrates, oxides, fluorides, chlorides, fluorinated chlorides, oxyfluorides, oxychlorides, oxyfluorinated chlorides and the like of these metals are supported. These metal compounds are particularly preferably used as nitrates or chlorides, and specifically, chromium nitrate, chromium chloride and the like are suitable.

担持触媒の調製方法としては特に限定されず、常温で液体の物質を担持する場合には担体に滴下、浸漬、スプレー等で吸着することができる。常温で固体物質を担持する場合には溶媒等に溶解し浸漬するか、スプレー等により吸着することができる。金属化合物が吸着担持された担体は、加熱、減圧してまたは加熱しながら減圧して過剰の溶媒等を除き乾燥した後、加熱下にフッ化水素、塩化水素、塩素、塩化フッ化炭化水素等により活性化を行い使用することができる。   The method for preparing the supported catalyst is not particularly limited, and when a liquid substance is supported at room temperature, it can be adsorbed onto the support by dripping, dipping, spraying, or the like. When a solid substance is supported at normal temperature, it can be dissolved in a solvent or the like and immersed, or adsorbed by spraying or the like. The carrier on which the metal compound is adsorbed and supported is heated, depressurized or depressurized while heating to remove excess solvent, etc., and then dried under heating, such as hydrogen fluoride, hydrogen chloride, chlorine, chlorofluorohydrocarbon, etc. Can be activated and used.

溶媒としては金属化合物を溶解し、反応により分解等を引き起こさない化合物であれば特に限定されず、たとえば水、メタノール、エタノール、イソプロパノール等のアルコール類、メチルエチルケトン、アセトン等のケトン類、酢酸エチル、酢酸ブチル等のカルボン酸エステル類、塩化メチレン、クロロホルム、トリクロロエチレン等のハロゲン系化合物、ベンゼン、トルエン等の芳香族類が挙げられる。水に溶解しにくい場合には、酸またはアルカリ等の溶解助剤を添加することにより溶解を促進することができる。   The solvent is not particularly limited as long as it is a compound that dissolves a metal compound and does not cause decomposition by the reaction. For example, water, alcohols such as methanol, ethanol, isopropanol, ketones such as methyl ethyl ketone, acetone, ethyl acetate, acetic acid Examples thereof include carboxylic acid esters such as butyl, halogen compounds such as methylene chloride, chloroform and trichloroethylene, and aromatics such as benzene and toluene. When it is difficult to dissolve in water, dissolution can be promoted by adding a dissolution aid such as acid or alkali.

何れの触媒も使用の前に所定の反応温度以上の温度で空焼きを行い反応中の触媒の組成変化等を防止することが有効である。また、反応中に微量の塩素、酸素または乾燥空気等の添加成分を反応器中に供給することは触媒寿命の延長、反応率、反応収率の向上に有効である。添加量としては、添加成分以外の成分の反応器への供給総量の１００容量％以下とするのが好ましい。これより多いと目的生成物の処理量が減少するので好ましくない。   It is effective to prevent any change in the composition of the catalyst during the reaction by baking it at a temperature equal to or higher than a predetermined reaction temperature before use. In addition, supplying a small amount of additional components such as chlorine, oxygen, or dry air into the reactor during the reaction is effective for extending the catalyst life, improving the reaction rate, and the reaction yield. The amount added is preferably 100% by volume or less of the total amount of components other than the added components supplied to the reactor. A larger amount is not preferable because the amount of the target product to be processed decreases.

反応温度は８０℃〜５００℃、好ましくは１５０℃〜４５０℃であり、より好ましくは２５０〜４００℃であり、反応温度８０℃よりも低い温度では反応が遅く実用的でない。反応温度が５００℃を越えると分解反応生成物が生成し、１−クロロ−３．３．３−テトラフルオロプロペンもしくは１，３，３，３−テトラフルオロプロペンの選択率またはそれらの選択率の合計が低下するので好ましくない。   The reaction temperature is 80 ° C. to 500 ° C., preferably 150 ° C. to 450 ° C., more preferably 250 ° C. to 400 ° C. The reaction is slow and impractical at a temperature lower than 80 ° C. When the reaction temperature exceeds 500 ° C., a decomposition reaction product is formed, and the selectivity of 1-chloro-3.3.3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene or the selectivity thereof is increased. Since the total is lowered, it is not preferable.

本発明の方法において、反応領域に供給する１，１，１，３，３−ペンタフルオロプロパン／塩化水素のモル比は反応温度、触媒等により変わり得るが１０／１〜１／５０、好ましくは１／１〜１／１０である。塩化水素が１，１，１，３，３−ペンタフルオロプロパンの５０モル倍を越えると同一反応器内における有機物処理量の減少並びに反応系から排出された未反応塩化水素と生成物の分離に支障をきたすので好ましくない。一方、塩化水素が１０モル倍以下の場合化学量論的に反応が起こり難いため反応率が低下し、収率が低下するので好ましくない。   In the method of the present invention, the molar ratio of 1,1,1,3,3-pentafluoropropane / hydrogen chloride supplied to the reaction zone may vary depending on the reaction temperature, catalyst, etc., but is preferably 10/1 to 1/50, preferably 1/1 to 1/10. When hydrogen chloride exceeds 50 mol times that of 1,1,1,3,3-pentafluoropropane, the amount of organic matter in the same reactor is reduced, and unreacted hydrogen chloride discharged from the reaction system is separated from the product. This is not preferable because it causes trouble. On the other hand, when hydrogen chloride is 10 mol times or less, the reaction hardly occurs stoichiometrically, so that the reaction rate decreases and the yield decreases, which is not preferable.

また、反応領域へは反応において活性でないガスを共存させることもできる。例えば、窒素、アルゴン、ヘリウムなどである。この様なガスは、反応成分である有機物および塩化水素の総容量に対し１倍未満とする。不活性ガスの存在は本発明にかかる反応では、減圧に相当するので好ましいが、１倍以上とするのは生成物の回収を困難としかつ過大の装置を必要とすることから生産性の低下を来すので好ましくない。   Further, a gas that is not active in the reaction can coexist in the reaction region. For example, nitrogen, argon, helium, etc. Such a gas should be less than 1 times the total volume of organic substances and hydrogen chloride as reaction components. The presence of the inert gas is preferable because it corresponds to reduced pressure in the reaction according to the present invention. However, the use of 1 or more times makes it difficult to recover the product and requires an excessive apparatus to reduce productivity. Since it comes, it is not preferable.

本発明の方法においては過剰量の塩化水素を使用することが好ましいことから通常、反応器排出ガスには未反応の塩化水素を伴うので、塩化水素は生成物から分離することで、本発明にかかる反応に再使用でき、または、塩酸として回収することもできる。   Since it is preferable to use an excess amount of hydrogen chloride in the process of the present invention, since the reactor exhaust gas is usually accompanied by unreacted hydrogen chloride, the hydrogen chloride is separated from the product, so that It can be reused in such reactions or can be recovered as hydrochloric acid.

本発明にかかる反応においては系内に存在する分子数が増加するため反応圧力は常圧あるいは減圧下で行うのが好ましいが通常は常圧（０．１Ｍｐａ）付近、例えば、０．０１〜１Ｍｐａで行うことができる。系内に存在する原料有機物、塩化水素が、反応系内で液化しないような温度、圧力条件を選ぶことが望ましい。接触時間は通常０．０１〜１０００秒、好ましくは０．１〜１００秒、より好ましくは１〜６０秒である。   In the reaction according to the present invention, since the number of molecules present in the system increases, the reaction pressure is preferably carried out under normal pressure or reduced pressure, but is usually near normal pressure (0.1 Mpa), for example, 0.01 to 1 Mpa. Can be done. It is desirable to select the temperature and pressure conditions so that the raw material organic matter and hydrogen chloride existing in the system do not liquefy in the reaction system. The contact time is usually 0.01 to 1000 seconds, preferably 0.1 to 100 seconds, more preferably 1 to 60 seconds.

反応器は、耐熱性とフッ化水素、塩化水素等に対する耐食性を有する材質で有れば良く、ステンレス鋼，ハステロイ、モネル、白金等が好ましい。また、これらの金属でライニングされた材料で製作することもできる。   The reactor may be made of a material having heat resistance and corrosion resistance against hydrogen fluoride, hydrogen chloride and the like, and stainless steel, hastelloy, monel, platinum and the like are preferable. It can also be made of materials lined with these metals.

本発明の方法により処理されて反応器より排出する１−クロロ−３，３，３−トリフルオロプロペンや１，３，３，３−テトラフルオロプロペンを含む排出ガスは、基本的に公知の方法で精製して製品とすることができる。   The exhaust gas containing 1-chloro-3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene treated by the method of the present invention and discharged from the reactor is basically a known method. Can be refined into a product.

精製方法としては限定されないが、例えば、塩化水素やフッ化水素を含む生成物は水で洗浄後、アルカリ性溶液で中和して塩化水素、フッ化水素等の酸性物質を除去し、ゼオライト等により乾燥し、有機物を蒸留するプロセスを採用することができる。また、塩化水素やフッ化水素を含む生成物を最初に硫酸で洗浄して、ついで、水で洗浄後、アルカリ性溶液で中和して塩化水素、フッ化水素等の酸性物質を除去し、ゼオライト等により乾燥し、有機物を蒸留するプロセスを採用することができる。さらに、塩化水素やフッ化水素を含む生成物をそのまま蒸留して、塩化水素、フッ化水素、１−クロロ−３，３，３−トリフルオロプロペン、１，３，３，３−テトラフルオロプロペンなどの成分に分離することもできる。   Although the purification method is not limited, for example, a product containing hydrogen chloride or hydrogen fluoride is washed with water and then neutralized with an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride. A process of drying and distilling organic matter can be employed. Also, products containing hydrogen chloride and hydrogen fluoride are first washed with sulfuric acid, then washed with water and neutralized with an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride. It is possible to employ a process of drying the organic matter and the like and distilling the organic matter. Further, the product containing hydrogen chloride or hydrogen fluoride is distilled as it is to obtain hydrogen chloride, hydrogen fluoride, 1-chloro-3,3,3-trifluoropropene, 1,3,3,3-tetrafluoropropene. It can also be separated into components such as

有機物成分の蒸留は、バッチ式で行うことも連続式で行うこともできる。ここでは第一段蒸留塔乃至第三段蒸留塔からなる三つの蒸留塔を用いて連続で行う場合について説明するが、さらに多段の蒸留塔群を用いる場合の手順やバッチ式での手順はこの説明から容易に知ることができる。第一段蒸留塔では低沸点のトランス−１，３，３，３−テトラフルオロプロペン（沸点−１９℃）を蒸留塔頂から回収し、第二段蒸留塔では第一段蒸留塔の缶出液を蒸留しトランス−１−クロロ−３，３，３−トリフルオロプロペンと１，１，１，３，３−ペンタフルオロプロパンの共沸混合物を蒸留塔頂から回収し、また、第三段蒸留塔では第二段蒸留塔の缶出液を蒸留精製することによりトランス−クロロ−３，３，３−トリフルオロプロペンを回収することができる。第三段蒸留塔の缶残液に含まれるシス−１−クロロ−３，３，３−トリフルオロプロペン等はさらに蒸留を繰り返すことによって回収することができる。   The distillation of the organic component can be performed batchwise or continuously. Here, a description will be given of a case where the three-stage distillation column consisting of the first-stage distillation column to the third-stage distillation column is used continuously, but the procedure for using a multi-stage distillation column group and the batch-type procedure are as follows. You can easily know from the explanation. In the first stage distillation column, low-boiling trans-1,3,3,3-tetrafluoropropene (boiling point -19 ° C.) is recovered from the top of the distillation column, and in the second stage distillation column, the first stage distillation column is taken out. The liquid was distilled to recover an azeotrope of trans-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane from the top of the distillation column. In the distillation column, trans-chloro-3,3,3-trifluoropropene can be recovered by distilling and purifying the bottoms of the second-stage distillation column. Cis-1-chloro-3,3,3-trifluoropropene and the like contained in the residual liquid of the third-stage distillation column can be recovered by further repeating distillation.

本発明の目的物のひとつである１−クロロ−３，３，３−トリフルオロプロペン（トランス体）は１，１，１，３，３−ペンタフルオロプロパンと共沸組成を形成し、蒸留精製が困難なため、できる限り１，１，１，３，３−ペンタフルオロプロパンの反応率を上げることが望ましい。   1-Chloro-3,3,3-trifluoropropene (trans form), which is one of the objects of the present invention, forms an azeotropic composition with 1,1,1,3,3-pentafluoropropane and is purified by distillation. Therefore, it is desirable to increase the reaction rate of 1,1,1,3,3-pentafluoropropane as much as possible.

第二段蒸留塔で共沸混合物として回収したトランス−１−クロロ−３，３，３−トリフルオロプロペンと１，１，１，３，３−ペンタフルオロプロパン混合物は、抽出蒸留などにより分離精製することもできるが、分離しないで再び反応系に原料として戻すことにより１，１，１，３，３−ペンタフルオロプロパンを目的物質１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンとすることができる。   The trans-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane mixture recovered as an azeotropic mixture in the second distillation column is separated and purified by extractive distillation or the like. However, 1,1,1,3,3-pentafluoropropane can be converted back to the reaction system again without separation to convert 1,1,1,3,3-pentafluoropropane into the target substance 1-chloro-3,3,3-trifluoropropene or 1, It can be 3,3,3-tetrafluoropropene.

以下、実施例により本発明を説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

［調製例１］
活性アルミナ（住友化学製ＮＫＨＤ−２４： 粒径２〜４ｍｍ、比表面積３４０ｍ2／ｇ）３００ｇを計り取り、表面に付着した粉を水洗した。フッ化水素１１５ｇを水１０３５ｇに溶解し、１０％フッ酸を調製した。洗浄した活性アルミナに１０％フッ酸を徐々に加え、攪拌後３時間静置した。ついで水洗し、ろ過した後、電気炉にて２００℃で２時間乾燥した。乾燥した活性アルミナ４００ｍｌを、熱媒循環装置に接続した外套を備えた円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径３．８ｃｍ、長さ４２ｃｍ）に充填し、窒素を流し、熱媒温度を２００℃に設定した。次いで、フッ化水素を窒素に同伴させて導入しフッ化水素／窒素モル比を１／１０〜１／５としてフッ化水素処理を行った。処理を行うにつれ活性アルミナの温度が上昇するが３５０℃を越えないようにフッ化水素と窒素の流量、比率を調節した。フッ素化による発熱が終了した時点で、熱媒温度を３５０℃に設定し、さらに２時間フッ化水素と窒素の流量を維持して、フッ素化アルミナ触媒の調製を完了した。 [Preparation Example 1]
300 g of activated alumina (NKHD-24 manufactured by Sumitomo Chemical Co., Ltd .: particle size 2 to 4 mm, specific surface area 340 m 2 / g) was weighed, and the powder adhering to the surface was washed with water. 115 g of hydrogen fluoride was dissolved in 1035 g of water to prepare 10% hydrofluoric acid. 10% hydrofluoric acid was gradually added to the washed activated alumina, and allowed to stand for 3 hours after stirring. Then, after washing with water and filtering, it was dried in an electric furnace at 200 ° C. for 2 hours. 400 ml of dried activated alumina is charged into a gas phase reactor (made of SUS316L, diameter 3.8 cm, length 42 cm) consisting of a cylindrical reaction tube equipped with a mantle connected to a heat medium circulation device, and nitrogen is flown to The medium temperature was set to 200 ° C. Subsequently, hydrogen fluoride was introduced with nitrogen fluoride, and a hydrogen fluoride treatment was performed at a hydrogen fluoride / nitrogen molar ratio of 1/10 to 1/5. The flow rate and ratio of hydrogen fluoride and nitrogen were adjusted so that the temperature of the activated alumina increased with the treatment but did not exceed 350 ° C. When the heat generation due to fluorination was completed, the heating medium temperature was set to 350 ° C., and the flow rates of hydrogen fluoride and nitrogen were maintained for 2 hours to complete the preparation of the fluorinated alumina catalyst.

［調製例２］
３００ｇの特級試薬Ｃｒ（ＮＯ3）・９Ｈ2Ｏを１リットルの水に溶かして水溶液とし、これに直径４〜８ｍｍ、比表面積１２００ｍ2／ｇ、細孔径１８Ａの粒状活性炭（日本エンバイロケミカル製、粒状白鷺Ｇ２Ｘ）１．８リットルを浸漬し、一昼夜放置した。ついで活性炭をろ過した後、熱風循環式乾燥機中で１００℃に保ち、さらに一昼夜乾燥した。得られたクロム担持活性炭のうち４００ｍｌを、熱媒循環装置に接続した外套を備えた円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径３．８ｃｍ、長さ４２ｃｍ）に充填し、窒素を流しながら熱媒温度を３００℃まで昇温した。水の排出が見られなくなった時点で、フッ化水素を窒素に同伴させながらフッ化水素／窒素モル比を１／１０〜１０／１としてフッ化水素処理を行った。熱媒温度を３５０℃まで上げ、さらにフッ化水素と窒素による処理状態を１時間維持しクロム担持活性炭触媒の調製を完了した。 [Preparation Example 2]
300 g of the special grade reagent Cr (NO 3 ) · 9H 2 O is dissolved in 1 liter of water to form an aqueous solution, and this is a granular activated carbon having a diameter of 4 to 8 mm, a specific surface area of 1200 m 2 / g, and a pore diameter of 18A (manufactured by Nippon Enviro Chemical, 1.8 liters of granular white birch G2X) was immersed and left for a whole day and night. Next, after the activated carbon was filtered, it was kept at 100 ° C. in a hot air circulating drier and further dried overnight. 400 ml of the obtained chromium-supported activated carbon was filled into a gas phase reactor (made of SUS316L, diameter 3.8 cm, length 42 cm) composed of a cylindrical reaction tube equipped with a jacket connected to a heat medium circulation device, and nitrogen was added. The heating medium temperature was raised to 300 ° C. while flowing. When water discharge was not observed, hydrogen fluoride treatment was performed with hydrogen fluoride / nitrogen molar ratio of 1/10 to 10/1 while entraining hydrogen fluoride with nitrogen. The heating medium temperature was raised to 350 ° C., and the treatment with hydrogen fluoride and nitrogen was maintained for 1 hour to complete the preparation of the chromium-supported activated carbon catalyst.

［調製例３］
３００ｇの特級試薬Ｃｒ（ＮＯ3）・９Ｈ2Ｏを１リットルの水に溶かして水溶液とし、これに調製例１と同様の方法でフッ酸浸漬後乾燥させた活性アルミナ１．８リットルを浸漬し、一昼夜放置した。ついで活性アルミナをろ過した後、熱風循環式乾燥機中で１００℃に保ち、さらに一昼夜乾燥した。得られたクロム担持アルミナ４００ｍｌを、熱媒循環装置に接続した外套を備えた円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径３．８ｃｍ、長さ４２ｃｍ）に充填し、窒素を流しながら３００℃まで昇温した。水の排出が見られなくなった時点で、フッ化水素を窒素に同伴させながらフッ化水素／窒素モル比を１／１０〜１０／１としてフッ化水素処理を行った。熱媒温度を３５０℃まで上げ、さらにフッ化水素と窒素による処理状態を１時間維持しクロム担持アルミナ触媒の調製を完了した。 [Preparation Example 3]
300 g of the special grade reagent Cr (NO 3 ) · 9H 2 O was dissolved in 1 liter of water to make an aqueous solution, and 1.8 liters of activated alumina that had been dipped in hydrofluoric acid and dried in the same manner as in Preparation Example 1 was immersed therein. I left it all day and night. Next, after the activated alumina was filtered, it was kept at 100 ° C. in a hot air circulating dryer and further dried overnight. 400 ml of the chromium-supported alumina thus obtained was filled into a gas phase reactor (made of SUS316L, diameter 3.8 cm, length 42 cm) composed of a cylindrical reaction tube equipped with a jacket connected to a heat medium circulation device, and nitrogen was allowed to flow. The temperature was raised to 300 ° C. When water discharge was not observed, hydrogen fluoride treatment was performed with hydrogen fluoride / nitrogen molar ratio of 1/10 to 10/1 while entraining hydrogen fluoride with nitrogen. The heating medium temperature was raised to 350 ° C., and the treatment state with hydrogen fluoride and nitrogen was maintained for 1 hour to complete the preparation of the chromium-supported alumina catalyst.

［参考調製例１］
直径４〜８ｍｍ、比表面積１２００ｍ2／ｇ、細孔径１８Ａの粒状活性炭（日本エンバイロケミカル製、粒状白鷺Ｇ２Ｘ）４００ｍｌを、熱媒循環装置に接続した外套を備えた円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径３．８ｃｍ、長さ４２ｃｍ）に充填し、窒素を流しながら熱媒温度を３００℃まで昇温した。水の排出が見られなくなった時点で、フッ化水素を窒素に同伴させながらフッ化水素／窒素モル比を１０／１としてフッ化水素処理を行った。熱媒温度を３５０℃まで上げ、さらにフッ化水素と窒素による処理状態を１時間維持し活性炭触媒の調製を完了した。 [Reference Preparation Example 1]
Gas phase consisting of a cylindrical reaction tube equipped with a mantle connected to a heat medium circulating device 400 ml of granular activated carbon (Nihon Enviro Chemical, granular white birch G2X) having a diameter of 4 to 8 mm, a specific surface area of 1200 m 2 / g, and a pore diameter of 18A The reactor (made of SUS316L, diameter 3.8 cm, length 42 cm) was filled, and the temperature of the heating medium was raised to 300 ° C. while flowing nitrogen. When water was no longer discharged, hydrogen fluoride treatment was performed with hydrogen fluoride / nitrogen molar ratio of 10/1 while entraining hydrogen fluoride with nitrogen. The heating medium temperature was raised to 350 ° C., and the treatment with hydrogen fluoride and nitrogen was maintained for 1 hour to complete the preparation of the activated carbon catalyst.

〔実施例１〕
熱媒循環装置に接続した外套を備えた円筒形反応管（ＳＵＳ３１６Ｌ製、直径３．８ｃｍ、長さ４２ｃｍ）からなる気相反応装置に、調製例１で調製したフッ素化アルミナ４００ｍｌを充填して反応を行った。約２００ｍｌ／分の流量で窒素ガスを流しながら反応管の温度を反応温度の３１０℃に設定し、反応管の温度が安定するまで待機した。温度が安定した後、塩化水素および１，１，１，３，３−ペンタフルオロプロパンをそれぞれ０．８ｇ／分および０．５ｇ／分の供給速度で反応管へ供給した。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ４９ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィー（FID検出器）で分析した結果、トランス−１，３，３，３−テトラフルオロプロペン５．１％（面積％。以下同じ。）、シス−１，３，３，３−テトラフルオロプロペン１．５％、１，１，１，３，３−ペンタフルオロプロパン１．０％、トランス−１−クロロ−３，３，３−トリフルオロプロペン８１．５％およびシス−１−クロロー３，３，３−トリフルオロプロペン１０．１％の組成であった。結果を表１に示す。 [Example 1]
A gas phase reactor composed of a cylindrical reaction tube (manufactured by SUS316L, diameter 3.8 cm, length 42 cm) having a mantle connected to a heat medium circulation device was charged with 400 ml of the fluorinated alumina prepared in Preparation Example 1. Reaction was performed. While flowing nitrogen gas at a flow rate of about 200 ml / min, the temperature of the reaction tube was set to the reaction temperature of 310 ° C. and waited until the temperature of the reaction tube was stabilized. After the temperature was stabilized, hydrogen chloride and 1,1,1,3,3-pentafluoropropane were fed into the reaction tube at feed rates of 0.8 g / min and 0.5 g / min, respectively.
After 2 hours from the start of the supply, the reaction was stable, and for 2 hours from that time, the product gas flowing out from the reaction tube was blown into water to remove the acid gas, and then passed through a container cooled with dry ice-acetone to give 49 g of product. Was collected. As a result of analyzing the collected product by gas chromatography (FID detector), trans-1,3,3,3-tetrafluoropropene 5.1% (area%, the same applies hereinafter), cis-1,3 , 3,3-tetrafluoropropene 1.5%, 1,1,1,3,3-pentafluoropropane 1.0%, trans-1-chloro-3,3,3-trifluoropropene 81.5% And cis-1-chloro-3,3,3-trifluoropropene of 10.1%. The results are shown in Table 1.



〔実施例２〕
塩化水素を０．３ｇ／分とし、１，１，１，３，３−ペンタフルオロプロパンを０．５ｇ／分の供給速度にした以外は、実施例１と同様にして反応を行った。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ４６ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィーで分析した結果、トランス−１，３，３，３−テトラフルオロプロペン２４．７％、シス−１，３，３，３−テトラフルオロプロペン５．２％、１，１，１，３，３−ペンタフルオロプロパン９．６％、トランス−１−クロロ−３，３，３−トリフルオロプロペン５３．３％およびシス−１−クロロ−３，３，３−トリフルオロプロペン６．６％の組成であった。結果を表１に示す。 [Example 2]
The reaction was carried out in the same manner as in Example 1 except that hydrogen chloride was 0.3 g / min and 1,1,1,3,3-pentafluoropropane was supplied at a feed rate of 0.5 g / min.
After 2 hours from the start of the supply, the reaction was stable, and for 2 hours from that time, the product gas flowing out from the reaction tube was blown into water to remove acidic gas, and then 46 g of product was passed through a container cooled with dry ice-acetone. Was collected. As a result of analyzing the collected product by gas chromatography, trans-1,3,3,3-tetrafluoropropene 24.7%, cis-1,3,3,3-tetrafluoropropene 5.2%, 9.6% 1,1,1,3,3-pentafluoropropane, 53.3% trans-1-chloro-3,3,3-trifluoropropene and cis-1-chloro-3,3,3- The composition was 6.6% trifluoropropene. The results are shown in Table 1.

〔実施例３〕
触媒として調製例２で調製したクロム担持活性炭触媒４００ｍｌを用い、反応温度を２８０℃とした以外は、実施例１と同様にして反応を行った。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ５２ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィーで分析した結果、トランス−１，３，３，３−テトラフルオロプロペン０．７％、シス−１，３，３，３−テトラフルオロプロペン０．２％、１，１，１，３，３−ペンタフルオロプロパン１．８％、トランス−１−クロロー３，３，３−トリフルオロプロペン８５．３％およびシス−１−クロロ−３，３，３−トリフルオロプロペン１０．０％の組成であった。結果を表１に示す。 Example 3
The reaction was performed in the same manner as in Example 1 except that 400 ml of the chromium-supported activated carbon catalyst prepared in Preparation Example 2 was used as the catalyst and the reaction temperature was 280 ° C.
After 2 hours from the start of the supply, the reaction was stable. Over the course of 2 hours, the product gas flowing out from the reaction tube was blown into water to remove the acidic gas, and then the product was passed through a container cooled with dry ice-acetone to give 52 g of product. Was collected. As a result of analyzing the collected product by gas chromatography, trans-1,3,3,3-tetrafluoropropene 0.7%, cis-1,3,3,3-tetrafluoropropene 0.2%, 1,1,1,3,3-pentafluoropropane 1.8%, trans-1-chloro-3,3,3-trifluoropropene 85.3% and cis-1-chloro-3,3,3-tri The composition was 10.0% fluoropropene. The results are shown in Table 1.

〔実施例４〕
触媒として調製例３で調製したクロム担持アルミナ触媒４００ｍｌを用い、反応温度を３５０℃とした以外は、実施例１と同様にして反応を行った。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ４９ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィーで分析した結果、トランス−１，３，３，３−テトラフルオロプロペン２．７％、シス−１，３，３，３−テトラフルオロプロペン０．５％、１，１，１，３，３−ペンタフルオロプロパン０．８％、トランス−１−クロロー３，３，３−トリフルオロプロペン８４．５％およびシス−１−クロロ−３，３，３−トリフルオロプロペン１０．１％の組成であった。結果を表１に示す。 Example 4
The reaction was carried out in the same manner as in Example 1 except that 400 ml of the chromium-supported alumina catalyst prepared in Preparation Example 3 was used as the catalyst and the reaction temperature was 350 ° C.
After 2 hours from the start of the supply, the reaction was stable, and for 2 hours from that time, the product gas flowing out from the reaction tube was blown into water to remove the acid gas, and then passed through a container cooled with dry ice-acetone to give 49 g of product. Was collected. As a result of analyzing the collected product by gas chromatography, trans-1,3,3,3-tetrafluoropropene 2.7%, cis-1,3,3,3-tetrafluoropropene 0.5%, 1,1,1,3,3-pentafluoropropane 0.8%, trans-1-chloro-3,3,3-trifluoropropene 84.5% and cis-1-chloro-3,3,3-tri The composition was 10.1% of fluoropropene. The results are shown in Table 1.

〔実施例５〕
塩化水素を０．５ｇ／分とし、有機物原料として１，１，１，３，３−ペンタフルオロプロパンおよびトランス−１−クロロ−３，３，３−トリフルオロプロペンをそれぞれ０．４ｇ／分および０．１ｇ／分の供給速度とした以外は、実施例１と同様にして反応を行った。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ５２ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィーで分析した結果、トランス−１，３，３，３−テトラフルオロプロペン１０．５％、シス−１，３，３，３−テトラフルオロプロペン２．２％、１，１，１，３，３−ペンタフルオロプロパン３．８％、トランス−１−クロロ−３，３，３−トリフルオロプロペン７５．２％およびシス−１−クロロ−３，３，３−トリフルオロプロペン８．２％の組成であった。結果を表１に示す。 Example 5
Hydrogen chloride is 0.5 g / min, and 1,1,1,3,3-pentafluoropropane and trans-1-chloro-3,3,3-trifluoropropene as organic raw materials are 0.4 g / min and The reaction was performed in the same manner as in Example 1 except that the supply rate was 0.1 g / min.
After 2 hours from the start of the supply, the reaction was stable. Over the course of 2 hours, the product gas flowing out from the reaction tube was blown into water to remove the acidic gas, and then the product was passed through a container cooled with dry ice-acetone to give 52 g of product. Was collected. As a result of analyzing the collected product by gas chromatography, trans-1,3,3,3-tetrafluoropropene 10.5%, cis-1,3,3,3-tetrafluoropropene 2.2%, 1,1,1,3,3-pentafluoropropane 3.8%, trans-1-chloro-3,3,3-trifluoropropene 75.2% and cis-1-chloro-3,3,3- The composition was 8.2% trifluoropropene. The results are shown in Table 1.

〔参考例１〕
触媒として比較調製例１で調製した活性炭４００ｍｌを用い、反応温度を２８０℃とした以外は、実施例１と同様にして反応を行った。
供給開始２時間後には反応が安定したので、その時から２時間にわたって、反応管から流出する生成ガスを水中に吹き込み酸性ガスを除去した後、ドライアイス−アセトンで冷却した容器に通じ５７ｇの生成物を捕集した。捕集した生成物をガスクロマトグラフィーで分析した結果、トランス−１，３，３，３−テトラフルオロプロペン０．１％、１，１，１，３，３−ペンタフルオロプロパン９９．８％、トランス−１−クロロー３，３，３−トリフルオロプロペン０．１％の組成であった。結果を表１に示す。 [Reference Example 1]
The reaction was carried out in the same manner as in Example 1 except that 400 ml of activated carbon prepared in Comparative Preparation Example 1 was used as a catalyst and the reaction temperature was 280 ° C.
After 2 hours from the start of the supply, the reaction was stabilized, and for 2 hours from that time, the product gas flowing out from the reaction tube was blown into water to remove the acid gas, and then 57 g of product was passed through a container cooled with dry ice-acetone. Was collected. As a result of analyzing the collected product by gas chromatography, trans-1,3,3,3-tetrafluoropropene 0.1%, 1,1,1,3,3-pentafluoropropane 99.8%, The composition was 0.1% trans-1-chloro-3,3,3-trifluoropropene. The results are shown in Table 1.

Claims (7)

気相中において固体触媒存在下１，１，１，３，３−ペンタフルオロプロパンを塩化水素と反応させることからなる１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 1-chloro-3,3,3-trifluoropropene or 1,3,3, comprising reacting 1,1,1,3,3-pentafluoropropane with hydrogen chloride in the gas phase in the presence of a solid catalyst A method for producing 3-tetrafluoropropene. 固体触媒が、アルミニウム、クロム、ジルコニウム、チタンおよびマグネシウムからなる群より選ばれる少なくとも１種の金属の金属酸化物である請求項１に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 The 1-chloro-3,3,3-trifluoropropene according to claim 1, wherein the solid catalyst is a metal oxide of at least one metal selected from the group consisting of aluminum, chromium, zirconium, titanium and magnesium. A method for producing 1,3,3,3-tetrafluoropropene. 固体触媒が、アルミニウム、クロム、チタン、マンガン、鉄、ニッケル、コバルト、マグネシウム、ジルコニウムおよびアンチモンからなる群より選ばれる少なくとも１種の金属の化合物またはその混合物を担体に担持した担持触媒である請求項１に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 The solid catalyst is a supported catalyst in which at least one compound of a metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, cobalt, magnesium, zirconium and antimony or a mixture thereof is supported on a support. A process for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to 1. 担体が、アルミニウム、クロム、ジルコニウム、チタンおよびマグネシウムからなる群より選ばれる少なくとも１種の金属の金属酸化物または活性炭である請求項３に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 The 1-chloro-3,3,3-trifluoropropene according to claim 3, wherein the support is a metal oxide or activated carbon of at least one metal selected from the group consisting of aluminum, chromium, zirconium, titanium and magnesium. Alternatively, a method for producing 1,3,3,3-tetrafluoropropene. １，１，１，３，３−ペンタフルオロプロパンが、１，１，１，３，３−ペンタフルオロプロパンと１−クロロ−３，３，３−トリフルオロプロペンの混合物として反応領域に供給される請求項１〜４のいずれか１項に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 1,1,1,3,3-pentafluoropropane is fed to the reaction zone as a mixture of 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene. A method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to any one of claims 1 to 4. １，１，１，３，３−ペンタフルオロプロパンが、請求項１に記載の製造方法による生成物から回収された１，１，１，３，３−ペンタフルオロプロパンまたは１−クロロ−３，３，３−トリフルオロプロペンを含む請求項１〜５のいずれか１項に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 1,1,1,3,3-pentafluoropropane is recovered from the product of the production method according to claim 1, 1,1,1,3,3-pentafluoropropane or 1-chloro-3, The method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene according to any one of claims 1 to 5, comprising 3,3-trifluoropropene. . 少なくとも原料の一部が１，１，１，３，３−ペンタフルオロプロパンと１−クロロ−３，３，３−トリフルオロプロペンを含む共沸混合物である請求項１〜６のいずれか１項に記載の１−クロロ−３，３，３−トリフルオロプロペンまたは１，３，３，３−テトラフルオロプロペンの製造方法。 The azeotropic mixture containing 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene at least a part of the raw material. A method for producing 1-chloro-3,3,3-trifluoropropene or 1,3,3,3-tetrafluoropropene as described in 1. above.
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